Entropy of aqueous surfaces. Application to polymeric Langmuir films.

Measuring surface (excess) entropies provides a bounty of valuable structural information that is hard to obtain otherwise. In the paper these quantities are defined and procedures of measurements discussed. Mostly they involve measurements at different temperatures. A review is given for interfaces with aqueous solutions in the absence of polymers. This review illustrates how, sometimes unanticipated, pieces of information are obtained, for example with cloud seeding and a possible explanation of the Jones-Ray effect. As a novel extension the procedure is applied to deposited, or Langmuir, monolayers of poly(ethylene oxide)-poly(propylene oxide) block copolymers. It will be shown how the various phase transitions and associated configurations of these polymers can be recognized and monitored.

Langmuir monolayers of non-ionic polymers: equilibrium or metastability? Case study of PEO and its PPO-PEO diblock copolymers.

Stability and reorganization in Langmuir films of PEO in PEO homopolymers and PPO-PEO block copolymers were investigated using film balance measurements. The apparent fractional losses of EO segments transferred into the subphase resulting from successive compression-expansion cycles have been estimated. The apparent loss is mainly Γ(max), M(n) and time-dependent. At surface concentrations Γ⩽0.32 mg/m(2), PEO films are in equilibrium. For 0.32⩽Γ⩽0.7 mg/m(2), the losses remain modest. Further compression leads to densification of the monolayer, requiring the interplay of thermodynamics and kinetic factors In the plateau regime, the loss is higher and constant for 1⩽Γ(max)⩽2 mg/m(2) upon maintaining the achieved surface area for 15 min. Similar losses were obtained for PEO homopolymers of high Mn and PPO353-PEO2295. It suggests that the PEO remains anchored in a metastable state at the air-water interface at surface concentration well above the onset of the plateau. Additional losses are incurred for PEO homopolymers for monolayers kept compressed in the plateau for 2 h. For the interpretation of these phenomena a combination of elements from self-consistent field theory and scaling is desirable with as a trend an increasing contribution of the latter with increasing surface concentration.

Phase transitions in polymer monolayers: Application of the Clapeyron equation to PEO in PPO-PEO Langmuir films.

In this paper we investigate the application of the two-dimensional Clapeyron law to polymer monolayers. This is a largely unexplored area of research. The main problems are (1) establishing if equilibrium is reached and (2) if so, identifying and defining phases as functions of the temperature. Once this is validated, the Clapeyron law allows us to obtain the entropy and enthalpy differences between two coexisting phases. In turn, this information can be used to obtain insight into the conformational properties of the films and changes therein. This approach has a wide potential for obtaining additional information on polymer adsorption at interfaces and the structure of their monolayer films. The 2D Clapeyron law was applied emphasizing polyethylene oxide (PEO) in polypropylene oxide (PPO)-PEO block copolymers, based on new well-defined data for their Langmuir films. Values for enthalpy per monomer of 0.12 and 0.23 kT were obtained for the phase transition of two different PEO chains (Neo of 2295 and 409, respectively). This enthalpy was estimated to correspond to 1.2±0.4 kT per EO monomer present in train conformation at the air/water interface.

Colloidal models. A bit of history.

This paper offers an anthology on developments in colloid and interface science emphasizing themes that may be of direct or indirect interest to Interfaces Against Pollution. Topics include the determination of Avogadro's number, development in the insight into driving forces for double layer formation, colloid stability, thin films, and thermodynamic approaches in interfacial electrochemistry. Some personal reminiscences of key players in the field are included, partly to illustrate historical developments.

Coagulation by multivalent counterions and the Schulze-Hardy rule.

Starting from a number of empirical papers by Matijevic et al., the issue of coagulation of hydrophobic colloids by multivalent inorganic counterions is revisited. More recent information is also considered, and some important trends are confirmed and made more quantitative. It can be concluded that the high coagulating power of multivalent ions is mostly not a direct result of their high valence but caused by their propensity of building complexes with water that adsorb specifically. This mechanism requires a revision of the Schulze-Hardy rule interpretations. In addition, this finding helps to define conditions where overcharging by multivalent counterions can be attributed to ion correlations.

Interfacial behaviour of proteins, with special reference to immunoglobulins. A physicochemical study.

Some basic elements of the adsorption of proteins on solid surfaces are briefly reviewed, emphasizing immunoglobulins. The paper focuses on the physicochemical interactions and considers the precautions that have to be taken to let the protein adsorb in a way in which it is biologically active. Contributing factors include surface pretreatment, composition of the solution, (pH, nature and concentration of electrolytes, etc.), extent of reversibility, and lateral interactions in the adsorbed state. Particular attention is paid to the option of partially pre-coating the adsorbent by irreversibly adsorbed polymers to induce the later adsorbing immune globulin molecules to assume a biologically preferred orientation and conformation.

Hydrolysis versus ion correlation models in electrokinetic charge inversion: establishing application ranges.

In this article, we investigate experimentally a wide range of situations where charge inversion (i.e., overcompensation of the surface charge of a colloidal particle by the countercharge) can occur. To that end, the electrophoretic mobility of sodium montmorillonite, silica, and polystyrene latex as functions of pH and concentration of different salts is presented, and conditions are established where charge inversion occurs. The reason for this study is to provide experimental evidence for distinguishing between two existing models for the explanation of charge inversion. One of these is the specific adsorption of ions located in the Stern layer in combination with a Gouy-Chapman diffuse part of the double layer. The other ion-correlation theories explain the phenomenon in terms of purely physical arguments based on Coulombic pair interactions between ions and surface charges and on excluded volume effects. In distinguishing between these two interpretations, the influence of the pH plays a central role because of its effect on the hydrolysis of multivalent cations. In our experiments, it is found that although 1-2 and 2-2 electrolytes provoke a decrease in the absolute values of the electrophoretic mobilities when their concentration in solution is increased, they never lead to charge inversion, whatever the surface charge or the pH. However, in the case of salts of trivalent cations, electrokinetic charge reversal is often observed above a certain critical electrolyte concentration. In addition, the extent of overcharging increases when the concentration is raised above the critical value. This trend occurs for any system in which the surface charge is pH-independent, as in polystyrene latex and montmorillonite. Most of the results presented here are compatible with the specific adsorption of hydrolyzed metal ions as the main driving force for charge inversion. At low pH, when the hydrolysis of trivalent cations is likely to be absent, overcharging can be attributed to ion correlation effects.

Surface tension of aqueous electrolyte solutions. Thermodynamics.

A thermodynamic theory is developed for obtaining the enthalpic and entropic contributions to the surface excess Gibbs energy of electrolyte solutions from the dependence of the surface tension on concentration and temperature. For elaboration, accurate activity coefficients in solution as functions of concentration and temperature are required. The theory is elaborated for (1-1) electrolytes and applied to HClO(4), HNO(3), NaCl, NaBr, and LiCl, of which the first two adsorb positively and the other three negatively. One of the conspicuous outcomes is that in all cases, the surface excess entropies slightly decrease with electrolyte activity but remain close to that of pure water, whereas the enthalpy is different from that. The implication is that the driving force for positive or negative adsorption must have an enthalpic origin. This finding can be useful in developing and evaluating theoretical models for the interpretation of surface tensions of electrolyte solutions.

The first step in layer-by-layer deposition: electrostatics and/or non-electrostatics?

A critical discussion is presented on the properties and prerequisites of adsorbed polyelectrolytes that have to function as substrates for further layer-by-layer deposition. The central theme is discriminating between the roles of electrostatic and non-electrostatic interactions. In order to emphasize this feature we refrain from discussing practical problems sometimes incurred in polyelectrolyte adsorption like freezing-in of non-equilibrium situations, patchwise attachment, unclear chemistry and only consider solid substrates. Although it is in principle ambiguous to discriminate between coulombic and non-coulombic or "chemical" interactions, it will be shown that, as a rule, non-coulombic contributions to the interactions cannot be neglected. They are responsible for the familiar overcharging. For obtaining more insight, it is recommended to consider electrometric techniques such as electrokinetics, conductometry and potentiometry, in combination with other analytical techniques applied to well-defined systems, for which various parameters can be modulated in a systematic way.

Adsorption of nonionic surfactants on cellulose surfaces: adsorbed amounts and kinetics.

Kinetic and equilibrium aspects of three different poly(ethylene oxide) alkylethers (C12E5, C12E7, C14E7) near a flat cellulose surface are studied. The equilibrium adsorption isotherms look very similar for these surfactants, each showing three different regions with increasing surfactant concentration. At low surfactant content both the headgroup and the tail contribute to the adsorption. At higher surface concentrations, lateral attraction becomes prominent and leads to the formation of aggregates on the surface. The general shape of the isotherms and the magnitude of the adsorption resemble mostly those for hydrophilic surfaces, but both the ethylene oxide and the aliphatic segments determine affinity for the surface. The adsorption and desorption kinetics are strongly dependent on surfactant composition. At bulk concentrations below the CMC, the initial adsorption rate is attachment-controlled. Above the CMC, the micellar diffusion coefficient and the micellar dissociation rate play a crucial role. For the most hydrophilic surfactant, C12E7, both parameters are relatively large. In this case, the initial adsorption rate increases with increasing surfactant concentration, also above the CMC. For C12E5 and C14E7 there is no micellar contribution to the initial adsorption rate. The initial desorption kinetics are governed by monomer detachment from the surface aggregates. The desorption rate constants scale with the CMC, indicating an analogy between the surface aggregates and those formed in solution.

Hetero-interaction between Gouy-Stern double layers: charge and potential regulation.

This issue of Advances is devoted to the memory of Hans-Joachim Schulze who, before his untimely death, made substantial contributions in the domains of flotation, wetting and particle interaction, often under adverse working conditions. Many of his publications involve hetero-interaction between different oxides or between solids and air bubbles. In the present paper, the theory for the electric interaction between charged interfaces is reviewed and extended by considering regulation on the Gouy-Stern level, including hetero-interaction. We start from a generalization of the phenomenon of regulation, distinguishing electrostatic, chemical and entropic contributions to the regulation capacity. The analysis is carried out in the mean field approximation for flat double layers. Against this background we review and discuss the existing literature. It is shown that for an appropriate account it is mandatory to include Stern layers, to which not only electrical but also chemical and entropic contributions to the regulation capacity can be attributed. It is demonstrated that interaction at constant diffuse double layer potential or -charge works only at rather large distance of separation. At shorter distance, substantial deviations from this behaviour are found, with a trend that interaction at (about) constant potential is the better obeyed the higher the corresponding regulation capacities are. A lattice model is elaborated to visualize the profiles of the (surface, Stern and diffuse) charges and the corresponding potential changes upon overlap, including the cases where strong induction leads to charge-inversion of the layer with the larger regulation capacity. A number of elaborations is presented, but the potentialities of the model are virtually unlimited.

Does electrical double layer formation lead to salt exclusion or to uptake?

When electric double layers are formed, cases have been reported where this formation involves expulsion of electrolyte into the solution and cases in which electrolyte is absorbed from the solution. Both situations are experimentally and theoretically documented, but they cannot be simultaneously correct. In this paper it is shown that this seeming conflict finds its cause in the way the double layer is formed: expulsion for double layers forming spontaneously by ion adsorption from the solution, but uptake when the double layer is formed by an external field. A thermodynamic analysis is presented.

Faradaic depolarization in the electrokinetics of the metal-electrolyte solution interface.

Streaming potentials (E(str)) have been measured in a flat thin-layer cell with gold and aluminum surfaces. The conventional relation between E(str) and the zeta-potential is shown to be applicable only as long as charge transfer reactions at the metal-electrolyte solution interface are insignificant in terms of the ensuing contribution to the overall cell conductivity. Owing to the irreversibility of the reduction/oxidation of water at most metal surfaces, streaming potentials can be obtained over a very broad range of pressure gradients for metallic substrates in electrolytes such as KNO3. The situation changes drastically in the presence of a reversible redox couple like Fe(CN)(6)3-/Fe(CN)(6)4-. Even small streaming potentials are then greatly diminished due to the extensive conduction that results from the bipolar electrolysis at the metal surface. For gold and aluminum in the presence of various electroinactive and electroactive electrolytes, the measured values for E(str) are shown to be consistent with their conventional voltammetric characteristics.